Use of a liquid dishwashing composition for cleaning persistent soil

Abstract

The invention relates to the use of liquid, phosphate-free dishwashing detergents that are free of bleaching agents and contain a polymer combination of polyaspartic acid or modified polyaspartic acid and graft polymers based on oligo- and polysaccharides, to improve cleaning performance, especially on stubborn carbohydrate-containing soils, particularly protein- and carbohydrate-containing, and especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

Description

[0001] The invention relates to the use of liquid, phosphate-free dishwashing detergents that are free of bleaching agents and contain a polymer combination of polyaspartic acid or modified polyaspartic acid and graft polymers based on oligo- and polysaccharides, to improve cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

[0002] It is known in the prior art that particularly difficult-to-remove soiling during dishwashing is caused by carbohydrates, especially starchy foods, remaining on the dishes, possibly in combination with protein-containing food residues, which have additionally dried, baked on, and / or baked on, particularly at higher temperatures and / or over longer periods. This soiling is often very firmly bonded to the items being washed and is very difficult to remove without scrubbing or high temperatures during the cleaning cycle and / or large amounts of detergent.

[0003] At the same time, consumers want to achieve sustainable, environmentally conscious, and as gentle a cleaning method as possible. For economic and environmental reasons, consumers typically wash heavily soiled items, such as casserole dishes or pots, which often have burnt-on and / or baked-on food residue, together with items that have more delicate surfaces, such as glass.

[0004] EP0423014 A1 discloses compositions that are effective against such soiling, but contain two different bleaching agent components.

[0005] WO 2019 / 211231 A1 describes compositions which contain a polymer mixture of polyaspartic acid or modified polyaspartic acid and graft polymers based on oligo- and polysaccharides solely for improving the shine of glassware during machine dishwashing.

[0006] WO2015 / 197379 A1 discloses formulations containing a complexing agent selected from GLDA and MGDA, and a graft copolymer based on oligo- and polysaccharides, which exhibit good coating inhibition.

[0007] Therefore, the object of the present invention is to overcome the disadvantages in the prior art and to provide an improvement in cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils, by means of a composition that is biodegradable and gentle on sensitive surfaces.

[0008] Surprisingly, it was found that the cleaning performance of liquid cleaning agents on such stubborn soiling improves when they contain a polymer combination according to the invention.

[0009] In a first aspect, the invention relates to the use of a phosphate-free, liquid dishwashing detergent formulation at 20 °C, which is free of bleaching agents, comprising, in each case based on the weight of the total composition, (i) 0.5 to 5 wt% of (a) at least one polyaspartic acid or modified polyaspartic acid or its salts, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably of 11:1 to 8:1, particularly preferably 11:1 to 9:1; (ii) 3 to 25 wt.-% Complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), ethylenediamine diacetic acid (EDDS) and / or their salts as complexing agents; (iii) 0.1 to 6 wt% thickening agent; (iv) at least 20 wt% water and (v) optionally 4 to 15 wt% builder and / or cobuilder; (vi) optionally 0.5 to 8 wt% non-ionic surfactants; (vii) 0.001 to 3 wt% enzymes; (viii) optionally 2 to 30 wt% organic solvents. for improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

[0010] The compositions used according to the invention offer better cleaning performance than other liquid dishwashing detergents without the polymer mixture on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

[0011] According to the invention, contaminants containing carbohydrates are those contaminants that contain mono-, di-, oligo- and / or polysaccharides.

[0012] Preferred mono- or disaccharides according to the invention are sucrose, glucose, fructose, dextrose or lactose.

[0013] Carbohydrate-containing soiling is also polysaccharide-containing soiling, the term polysaccharide being explained in more detail below. Particularly important polysaccharide-containing, especially starch-containing, soiling according to the invention is that which results from baking or cooking starch-containing products such as pasta, oatmeal, bread, cakes, and the like, especially spaghetti, and in particular dried and / or burnt-on spaghetti residue.

[0014] Stubborn soiling is particularly defined as soiling where the soiling, especially food residue, has dried over a longer period of time, especially due to higher temperatures and / or prolonged baking and / or caking on.

[0015] The formulation used according to the invention is particularly effective on dried-out (e.g., oat flakes), baked-on and / or burnt-on carbohydrate-containing food residues, such as caramel, crème brûlée and spaghetti.

[0016] According to the invention, protein- and carbohydrate-containing soiling is understood to mean soiling that contains both proteins and carbohydrates.

[0017] According to the invention, protein-containing soiling is preferably that which contains meat, egg and / or milk, in particular egg and / or milk. It is particularly noticeable with foods containing egg and / or milk and carbohydrates that such soiling cannot be removed completely.

[0018] Surprisingly, it was found that the compositions used according to the invention significantly improved the cleaning performance on crème brûlée, which is a common type of protein- and carbohydrate-containing soiling that is further baked on or burnt on due to the preparation process. Furthermore, the compositions used according to the invention resulted in particularly significant improvements in cleaning performance on spaghetti, especially on spaghetti that is baked on.

[0019] Furthermore, the compositions are advantageous because their biodegradability is improved. Preferably, the active ingredients of the compositions are biodegradable, resulting in a high percentage of biodegradability, preferably over 85% by weight of the composition. This means that 85% by weight of the components of the composition are biodegradable. Preferably, more than 90% by weight of the composition is biodegradable, and particularly preferably, more than 98% of the composition is biodegradable. The biodegradability of the components is defined according to OECD 301.

[0020] The dishwashing detergent formulations used according to the invention are particularly suitable as dishwashing detergent compositions for machine dishwashing. In one embodiment, the dishwashing detergent formulation according to the invention is therefore a machine dishwashing detergent composition. The dishwashing detergent formulations used according to the invention can be provided in liquid or gel form, as one or more phases.

[0021] Preferred embodiments are described in the dependent claims.

[0022] Where wt.% values ​​are given, they refer to the total weight of the liquid composition unless explicitly stated otherwise. Numerical ranges in the format "from x to y" include the values ​​mentioned above. If several preferred numerical ranges are given in this format, all ranges resulting from the combination of the different endpoints are also included.

[0023] In the present description, the terms "ein" and "eine" as well as "at least one" are synonymous with the term "one or more" and can be used interchangeably.

[0024] "One or more," as used here, refers to at least one and includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or more of the types mentioned. Similarly, "at least one," as used here, refers to, but is not limited to, 1, 2, 3, 4, 5, 6, and more. With regard to an ingredient, it refers to the type of ingredient and not the absolute number of molecules. Thus, "at least one surfactant," for example, means at least one type of surfactant; that is, it could refer to one type of surfactant or a mixture of several different surfactants. Along with the weight specifications, the statement refers to all compounds of the specified type contained in the composition / mixture; that is, the composition contains no further compounds of that type beyond the specified quantity of the corresponding compounds.

[0025] When molar masses are referenced here, these values ​​always refer to the number-average molar mass Mn, unless explicitly stated otherwise. The number-average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as the eluent. The weight-average molar mass Mw can also be determined by GPC as described for Mn.

[0026] When alkaline earth metals are mentioned below as counterions to monovalent anions, this means that the alkaline earth metal is naturally present in only half the amount of substance as the anion – which is sufficient for charge balance.

[0027] In the context of the present invention, unless otherwise specified, fatty acids or fatty alcohols or their derivatives are understood to be branched or unbranched carboxylic acids or alcohols or their derivatives, preferably with 6 to 22 carbon atoms. The former are preferred for ecological reasons, particularly because of their plant-based origin from renewable raw materials, without, however, limiting the teaching of the invention to them. In particular, oxo alcohols or their derivatives, obtainable, for example, by the ROELEN oxo synthesis, can also be used accordingly.

[0028] The cleaning composition according to the invention is provided in the form of a liquid. The term "liquid," as used herein, includes liquids and gels. The term "liquid," as used herein, refers to compounds or mixtures of compounds that are free-flowing and pourable at 20°C and 1 bar.

[0029] The cleaning agent according to the invention is phosphate-free. "Phosphate-free" here means that the cleaning agent is essentially free of phosphate (including orthophosphate, polyphosphate and / or pyrophosphate), in particular with phosphates in an amount of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total weight of the composition.

[0030] The expression "essentially free of" means that the respective compound may, in principle, be present, but then only in an amount that does not impair the function of the other components. Within the scope of the present invention, the property "essentially free of" a particular compound is therefore preferably understood to mean a total weight of less than 0.1 wt.%, more preferably less than 0.001 wt.%, and in particular, free of it, based on the total weight of the composition. It is particularly preferred if no amount of this compound has been intentionally added.

[0031] The cleaning composition according to the invention is bleach-free. Within the scope of the invention, this means that the compositions contain less than 0.1 wt.% of percarbonate salts, alkali hypochlorite, and their precursors, based on the total weight of the composition. Preferably, the compositions contain less than 0.01 wt.%, and even more preferably less than 0.001 wt.% of these components, based on the total weight of the composition.

[0032] The term "bleach-free" means that the cleaning agent is essentially free of active ingredients capable of releasing bleaching agents, in particular peroxide-containing compounds, hypohalogenated compounds, or H₂O₂, into the wash liquor in an automatic dishwasher. In a preferred embodiment, "bleach-free" means that the composition contains bleaching compounds (compounds that release bleaching agents) in an amount of less than 0.1% by weight, preferably less than 0.01% by weight, based on the total weight of the composition.

[0033] It was surprisingly found that liquid compositions containing a polymer mixture according to i) containing biodegradable polyaspartic acid or modified polyaspartic acid or their salts (a) and biodegradable graft polymer (b) produced by grafting at least one ethylene unsaturated mono- or dicarboxylic acid and at least one N-containing cationic monomer onto oligo- and polysaccharides result in a greatly improved cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-in carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-in protein- and carbohydrate-containing soils.

[0034] The weight ratio of aspartic acid or modified aspartic acid (a) to graft polymer (b) is 18:1 to 5:1, more preferably 11:1 to 8:1, particularly preferably 11:1 to 9:1.

[0035] The sum of components (a) and (b) constitutes 0.5 to 5.0 wt.%, based on the weight of the total composition. In the formulation of the dishwashing detergent formulation used according to the invention, components (a) and (b) can be added separately or as a premixed film-inhibiting composition.

[0036] In a preferred embodiment, the amount of component according to (i) in the dishwashing detergent formulation is 1.0% to 4.5%, preferably 1.2% to 4.0%, based on the weight of the total composition.

[0037] Polyaspartic acid is known as a biodegradable, dispersing, and scale-inhibiting polymer. A modified polyaspartic acid, which can be used according to the present invention, can be prepared by polycondensation of (a1) 50 to 99 mol%, preferably 60 to 95 mol%, particularly preferably 80 to 95 mol%, aspartic acid; and (a2) 1 to 50 mol%, preferably 5 to 40 mol%, particularly preferably 5 to 20 mol%, at least one compound containing carboxyl groups, and subsequent hydrolysis of the co-condensates upon addition of a base, e.g., sodium hydroxide, wherein (a2) is not aspartic acid.

[0038] The carboxyl-containing compound (a2) used in connection with the production of the polyaspartic acid to be used according to the invention can be, among other things, a carboxylic acid (mono- or polycarboxylic acid), a hydroxycarboxylic acid and / or an amino acid (other than aspartic acid). Such carboxylic acids or hydroxycarboxylic acids are preferably polybasic. In this context, polybasic carboxylic acids can therefore be used in the production of the polyaspartic acid to be used according to the invention, e.g. B. Oxalic acid, adipic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, succinic acid, malonic acid, succinic acid, azelaic acid, diglycolic acid, glutaric acid, C1-C26 alkyl succinic acids (e.g. octyl succinic acid), C2-C26 alkenyl succinic acids (e.g. octenyl succinic acid), 1,2,3-propanetricarboxylic acid, 1,1,3,3-propanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,3-propanetetracarboxylic acid or 1,3,3,5-pentanetetracarboxylic acid.In addition, polybasic hydroxycarboxylic acids can also be used in this context, e.g. citric acid, isocitric acid, mucilage acid, tartaric acid, tartronic acid (hydroxymalonic acid) or malic acid. Amino acids that can be used in this context include, among others, aminocarboxylic acids (e.g., glutamic acid, cysteine), basic diaminocarboxylic acids (e.g., lysine, arginine, histidine, aminocaprolactam), neutral amino acids (e.g., glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (e.g., taurine), hydroxylaminoic acids (e.g., hydroxyproline, serine, threonine), iminocarboxylic acids (e.g., proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g., anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid.Preferred carboxyl-containing compounds (a2) in connection with the preparation of the modified polyaspartic acids to be used according to the invention are 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, particularly preferably 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.

[0039] The molecular weight (Mw) of the (modified) polyaspartic acid can be easily adjusted by varying the reaction conditions. Molecular weights between 1000 g / mol and 100,000 g / mol can be achieved by simply adjusting the process parameters (temperature, catalyst, reaction time).

[0040] The preferred molecular weight of the (modified) polyaspartic acid used according to the invention is in the range between 1000 g / mol and 20,000 g / mol, preferably between 1500 and 15,000 g / mol and particularly preferably between 2000 and 10,000 g / mol.

[0041] The aspartic acid used in connection with the production of the (modified) polyaspartic acid to be used according to the invention can be either L- or D- and DL-aspartic acid. L-aspartic acid is preferably used.

[0042] In a preferred embodiment, the dishwashing detergent formulation contains polyaspartic acid as a homopolymer in the above-mentioned amounts and molecular weights.

[0043] The preparation of the (modified) polyaspartic acids to be used according to the invention is generally carried out via a poly(co)condensation of aspartic acid, optionally with at least one carboxyl-containing compound (not aspartic acid), and subsequent hydrolysis of the resulting (co)condensates with the addition of a base, as shown and described above and below. The preparation of such (modified) polyaspartic acids is also described, for example, in DE 4221875.6 or WO 2019 / 211231 A1, to whose disclosures reference is hereby made in full.

[0044] In the case of treatment with bases, neutralized (modified) polyaspartic acid is obtained in the form of the salts corresponding to the bases. The (modified) polyaspartic acids and / or their salts to be used according to the invention can be used as an aqueous solution or in solid form, e.g., in powder or granule form. As is known to those skilled in the art, the powder or granule form can be obtained, for example, by spray drying, spray granulation, fluidized bed spray granulation, roller drying, or freeze-drying of the aqueous solution of the polyaspartic acids or their salts.

[0045] The composition according to the invention comprises (b) at least one graft copolymer consisting of (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene unsaturated N-containing monomer with a permanent cationic charge.

[0046] Oligosaccharides, as defined in the present invention, are carbohydrates with three to ten monosaccharide units per molecule, e.g., glycans. Polysaccharides, as defined in the present invention, are carbohydrates with more than ten monosaccharide units per molecule. Oligosaccharides and polysaccharides can be, for example, linear, cyclic, or branched.

[0047] Examples of polysaccharides include biopolymers such as starch and glycogen, as well as cellulose, dextran, and tunicin. Inulin, a polycondensate of D-fructose (fructans), chitin, and alginic acid are also examples. Further examples of polysaccharides are starch degradation products, such as those obtained through the enzymatic or chemical breakdown of starch. Examples of chemical starch degradation include oxidative degradation and acid-catalyzed hydrolysis.

[0048] Preferred examples of starch degradation products are maltodextrins and glucose syrup. Within the scope of the present invention, the term maltodextrin is used for mixtures of monomers, dimers, oligomers, and polymers of glucose. The percentage composition varies depending on the degree of hydrolysis. This is described by the dextrose equivalent, which in the case of maltodextrin ranges from 3 to 40.

[0049] Preferably, the graft base (b1) is selected from polysaccharides, in particular from starch, which is preferably not chemically modified. In one embodiment of the present invention, the starch is selected from polysaccharides containing between 20 and 30 wt.% amylose and between 70 and 80 wt.% amylopectin. Examples are corn starch, rice starch, potato starch, and wheat starch. The side chains are grafted onto the graft base (b1). Preferably, on average, one to ten side chains can be grafted onto each molecule of the graft copolymer (b). Preferably, a side chain is linked to the anomeric carbon atom of a monosaccharide or to an anomeric carbon atom of the chain end of an oligo- or polysaccharide. The number of side chains is limited from the top by the number of carbon atoms with hydroxyl groups in the graft base (b1) in question.

[0050] Examples of monocarboxylic acids (b2) are ethylene-unsaturated C3-C10 monocarboxylic acids and their alkali or ammonium salts, in particular the potassium and sodium salts. Preferred monocarboxylic acids (b2) are acrylic acid and methacrylic acid, but also sodium (meth)acrylate. Mixtures of ethylene-unsaturated C3-C10 monocarboxylic acids, and in particular mixtures of acrylic acid and methacrylic acid, are also preferred components (b2).

[0051] Examples of dicarboxylic acids (b2) are ethylene unsaturated C4-C10 dicarboxylic acids and their mono- and especially dialkali or ammonium salts, in particular the dipotassium and disodium salts, as well as anhydrides of ethylene unsaturated C4-C10 dicarboxylic acids.

[0052] Preferred dicarboxylic acids (b2) are maleic acid, fumaric acid, itaconic acid, maleic anhydride and itaconic anhydride.

[0053] In one embodiment, the graft copolymer (b) contains, in addition to the monomer (b3), at least one monocarboxylic acid (b2) and at least one dicarboxylic acid (b2) in at least one side chain. In a preferred embodiment of the present invention, the graft copolymer (b) in its polymerized form comprises, in addition to the monomer (b3), exclusively monocarboxylic acid (b2) but no dicarboxylic acid (b2) in the side chain.

[0054] Examples of monomers (b3) are ethylene-unsaturated nitrogen-containing compounds with a permanent cationic charge, i.e., those ethylene-unsaturated nitrogen-containing compounds that react with anions such as sulfate, C1-C4 alkyl sulfates, and halides, especially chloride, to form ammonium salts, regardless of pH. Any mixture of two or more monomers (b3) is also suitable.

[0055] Examples of suitable monomers (b3) are the appropriately quaternized derivatives of vinyl- and allyl-substituted nitrogen heterocycles such as 2-vinylpyridine and 4-vinylpyridine, 2-allylpyridine and 4-allylpyridine, as well as N-vinylimidazole, e.g., 1-vinyl-3-methylimidazolium chloride. Also suitable are the appropriately quaternized derivatives of N,N-diallylamines and N,N-diallyl-N-alkylamines, such as N,N-diallyl-N,N-dimethylammonium chloride (DADMAC).

[0056] In one embodiment of the present invention, the monomer (b3) is selected from appropriately quaternized, ethylene-unsaturated amides of mono- and dicarboxylic acids with diamines having at least one primary or secondary amino group. In another embodiment of the present invention, the monomer (b3) is selected from appropriately quaternized, ethylene-unsaturated esters of mono- and dicarboxylic acids with C2-C12 amino alcohols that are mono- or dialkylated at the amine nitrogen.

[0057] Suitable acid components of the aforementioned esters and amides include, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate, and mixtures thereof. Acrylic acid, methacrylic acid, and mixtures thereof are preferably used as the acid component.

[0058] Preferred monomers (b3) have the general formula (I), where the variables are defined as follows: Z is O or NR1, R1 is selected from methyl and hydrogen, A1 is selected from C2-C4 alkylenes, R2 are the same or different and selected from Ci-C4 alkyl, X is selected from halide, mono-Ci-C4 alkyl sulfate and sulfate.

[0059] Particularly preferred monomers (b3) are trialkylaminoethyl (meth)acrylatochloride or -alkyl sulfate and trialkylaminopropyl (meth)acrylatochloride or -alkyl sulfate as well as (meth)acrylamidoethyl trialkylammonium chloride or -alkyl sulfate and (meth)acrylamidopropyl trialkylammonium chloride or -alkyl sulfate, wherein the respective alkyl group is preferably methyl or ethyl or mixtures thereof.

[0060] Particularly preferred is (Meth)acrylamidopropyltrimethylammonium halide, especially acrylamidopropyltrimethylammonium chloride ("APT AC") or methacrylamidopropyltrimethylammonium chloride ("MAPTAC").

[0061] In a further preferred embodiment of the present invention, the monomer (b3) is selected from trimethylammonium-C 2 -C 3 -alkyl(meth)acrylatohalide, in particular 2-(trimethylamino)ethyl(meth)-acrylatochloride and 3-(trimethylamino)propyl(meth)acrylatochloride.

[0062] In the preferred embodiment of the present invention, the monomer (b3) is trimethylaminoethyl(meth)acrylatochloride or methacrylamidopropyltrimethylammonium chloride, preferably ω-trimethylaminoethyl(meth)acrylatochloride.

[0063] The graft copolymer (b) in its polymerized form may contain at least one further comonomer (b4) in one or more side chains, e.g., hydroxyalkyl esters such as 2-hydroxyethyl(meth)acrylate or 3-hydroxypropyl(meth)acrylate, or esters of alkoxylated fatty alcohols, or sulfonic acid group-containing comonomers, e.g., 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its alkali metal salts. Preferably, the graft copolymer (b) contains no further comonomers (b4) in one or more side chains other than the monomer (b3) and the monocarboxylic acid (b2) or dicarboxylic acid (b2).

[0064] In one embodiment of the present invention, the proportion of the graft base (b1) in the graft copolymer (b) is in the range of 40 to 95 wt.%, preferably 50 to 90 wt.%, in each case based on the total graft copolymer (b). In another embodiment of the present invention, the proportion of monocarboxylic acid (b2) or dicarboxylic acid (b2) is in the range of 2 to 40 wt.%, preferably 5 to 30 wt.% and particularly 5 to 25 wt.%, in each case based on the total graft copolymer (b).

[0065] The monomers of type (b3) are polymerized in amounts of 5 to 50 wt.%, preferably 5 to 40 wt.% and particularly preferably 5 to 30 wt.%, in each case based on the total graft copolymer (b).

[0066] It is preferred if the graft copolymer (b) in polymerized form contains more monocarboxylic acid (b2) than compound (b3), based on the molar proportions, for example in the range of 1.1 :1 to 5:1, preferably 2:1 to 4:1.

[0067] In one embodiment of the present invention, the average molecular weight (Mw) of the graft copolymer (b) is in the range of 2000 to 200,000 g / mol, preferably from 5000 to 150,000 g / mol, and particularly in the range of 8000 to 100,000 g / mol. The average molecular weight Mw is preferably measured by gel permeation chromatography in aqueous KCl / formic acid solution.

[0068] Graft copolymer (b) can preferably be obtained as an aqueous solution from which it can be isolated, e.g. by spray drying, spray granulation or freeze-drying.

[0069] If desired, a solution of the graft copolymer (b) or dried graft copolymer (b) can be used to prepare the formulations used according to the invention.

[0070] The monomer (b3) itself can be polymerized to form a graft copolymer (b) or a non-quaternized equivalent, in the case of APT AC for example. and in the case of MAPTAC with and after copolymerization an alkylation can take place, e.g. with C1-C8 alkyl halide or di-C1-C4 alkyl sulfate, e.g. with ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate or diethyl sulfate.

[0071] A preferred embodiment of the dishwashing detergent formulation used according to the invention is that the monomer (b3) is at least one compound of the general formula (I), where the variables are defined as follows: Z is O or NR1, preferably ZO, R1 is selected from methyl and hydrogen, A1 is selected from C2-C4 alkylenes, R2 are the same or different and selected from C1-C4 alkyl, X< is selected from halide, mono-C1-C4 alkyl sulfate and sulfate.

[0072] Particularly preferred are monomers (b3) according to the above formula (I) wherein R 2< is methyl and A1 is CH 2 CH 2 and X -< is chloride.

[0073] The composition according to the invention, consisting of polyaspartic acid or modified polyaspartic acid (a) and graft copolymer (b), as described herein and to be used according to the invention, can be used particularly advantageously in machine dishwashing detergents.

[0074] They are particularly distinguished by their film-inhibiting effect against both inorganic and organic films. Specifically, they inhibit films made of calcium and magnesium carbonate, as well as calcium and magnesium phosphates and phosphonates. Additionally, they prevent deposits originating from the dirt components of the washing solution, such as grease, protein, and starch films.

[0075] The dishwashing detergent formulation used according to the invention contains 3 to 25 wt% of the total composition of complexing agents selected from the group consisting of citric acid or its salts, methylglycine diacetic acid (MGDA) and / or its salts, ethylenediamine diacetic acid (EDDS) and / or its salts, and glutamic acid diacetic acid (GLDA) or its salts.

[0076] Particularly preferred representatives of this class are their alkali metal salts, especially the trisodium salt of methylglycine diacetic acid (MGDA), the disodium salt of ethylenediamine diacetic acid (EDDS), the tetrasodium salt of glutamic diacetic acid (GLDA) and / or trisodium citrate, especially anhydrous trisodium citrate or trisodium citrate dihydrate.

[0077] Combinations of citric acid and / or its salts with methylglycine diacetic acid (MGDA) or its salts are also preferred. The combination of trisodium salt of methylglycine diacetic acid (MGDA) and trisodium citrate is particularly preferred.

[0078] In another embodiment, combinations of citric acid and / or its salts with ethylenediaminediacetic acid (EDDS) or its salts are also preferred. The combination of disodium salt of ethylenediaminediacetic acid (EDDS) and trisodium citrate is particularly preferred.

[0079] In a preferred embodiment of the composition, the dishwashing detergent formulation is characterized in that the amount of methylglycine diacetic acid (MGDA) and its salts constitutes 4.5 to 20 wt.%, in particular 5 to 20 wt.% of the total composition.

[0080] In another preferred embodiment of the composition, the dishwashing detergent formulation is characterized in that the amount of citric acid and its salts constitutes 0.5 to 15 wt.% of the total composition.

[0081] In a preferred embodiment of the composition, the dishwashing detergent formulation is characterized in that the amount of methylglycine diacetic acid (MGDA) and its salts is 4.5 to 20 wt.% of the total composition and the amount of citric acid and its salts is 0.5 to 15 wt.% of the total composition.

[0082] The compositions used according to the invention contain 0.1 to 6% by weight, based on the weight of the total composition, of thickening agent. Preferably, the thickening agent is selected from the group consisting of polysaccharides, preferably thickening polysaccharides (or polysaccharide thickeners), such as xanthan gum, guar gum, carrageenan, pectin, alginate, carboxymethylcellulose and succinoglycan gum, in particular polysaccharide gums, synthetic rheology modifiers based on acrylates (such as Carbopol® < Aqua 30, Acusol® < 810, Acusol® < 830, Acusol® < 835 or Acusol® < 842) or urethanes (such as Acusol® < 880 and Acusol® < 882); "low molecular weight gelators" ("LMWG"), such as dibenzylidene sorbitol (DBS), hydrogenated castor oil (HCO3), urea derivatives (such as Rheobyk® < 7420) or cyclic dipeptides.

[0083] Particularly preferred are cleaning agents containing 0.15 to 5.0 wt.%, preferably 0.18 to 2.5 wt.%, preferably 0.2 to 1.5 wt.%, most preferably 0.25 to 1.0 wt.%, based on the weight of the liquid phase, thickening agents.

[0084] Preferred thickening agents are selected from the group of polysaccharides, preferably thickening polysaccharides (or polysaccharide thickeners), in particular xanthan gum, cross-linked polyacrylates and urea derivatives.

[0085] Xanthan gum, urea derivatives such as Rheobyk® < 7420 and / or cross-linked polyacrylate such as Acusol® < 810 are able to stabilize the liquid phase and minimize the disintegration of this mixture. In particular, they reduce the sedimentation of the detergent components.

[0086] In a preferred embodiment, the dishwashing detergent formulation according to the invention contains xanthan gum as a thickening agent, preferably in an amount of 0.2 to 0.8 wt.% of the total composition.

[0087] The cleaning composition according to the invention contains a significant amount of water. In a preferred embodiment of the invention, the amount of water is at least 30% by weight of the total composition, preferably 40 to 70% by weight of the total composition, and most preferably 40 to 60% by weight of the total composition.

[0088] In a preferred embodiment of the invention, the cleaning agent contains 45 to 75 wt.% water and 0.15 to 2.5 wt.% thickening agents, each based on the weight of the composition. More preferably, it contains 50 to 70 wt.% water and 0.2 to 1.5 wt.% thickening agents, preferably selected from xanthan gum, each based on the weight of the composition.

[0089] Builders and / or co-builders according to the invention (referred to as components (v) in the main claim) that can be used are, in particular, water-soluble or water-insoluble substances whose main function is the binding of calcium and magnesium ions. These are not ingredients that are not identical to the ingredients referred to as component (ii).

[0090] The terms "builder" and "cobuilder" used according to the invention therefore do not include citric acid, ethylenediaminediacetic acid (EDDS), methylglycinediacetic acid (MGDA), glutamic diacetic acid (GLDA) and / or their salts. The builders and / or cobuilders may be low molecular weight carboxylic acids and their salts, e.g., alkali metal malonates, fatty acid sulfonates, gluconic acids, oxodiacetate, carboxymethyloxysuccinates, tartrate monoacetate, tartrate diacetate and α-hydroxypropionic acid.

[0091] Other building materials that can be used in conjunction with the dishwashing detergent formulations used according to the invention are carbonates and hydrocarbons, of which alkali salts, in particular sodium salts, are preferred.

[0092] In a preferred embodiment, the dishwashing detergent formulation is characterized in that the composition contains an alkali metal carbonate as a builder (a component according to (v) of the main claim) in a quantity of 5 to 12 wt.%, preferably 7 to 10 wt.% of the total composition.

[0093] Another cobuilder that may be included in some embodiments of the cleaning agent used according to the invention is phosphonates. These are, in particular, hydroxyalkane and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as its sodium salt, with the disodium salt giving a neutral reaction and the tetrasodium salt giving an alkaline reaction (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and higher homologs thereof. They are preferably used in the form of their reaction-neutral sodium salts, e.g., as the hexasodium salt of EDTMP or as the heptasodium and octanosodium salts of DTPMP. The builder used here from the class of phosphonates is preferably HEDP (especially as an alkali metal salt, and particularly preferably as a sodium salt).Furthermore, aminoalkane phosphonates have a pronounced heavy metal binding capacity.

[0094] In a highly preferred embodiment, the composition contains less than 0.1%, preferably less than 0.01% by weight, of phosphonates. Preferably, the composition contains less than 0.01% by weight of phosphorus-containing compounds. Phosphonate-free compositions exhibit better biodegradability and / or are preferable from an environmental perspective. Therefore, these embodiments are particularly preferred.

[0095] In a preferred embodiment of the invention, the formulations are essentially free of silicates. Preferably, the total weight of the silicates is less than 0.1 wt.%, more preferably less than 0.001 wt.%, and in particular free of them, based on the total weight of the composition.

[0096] Copolymers of acrylic or methacrylic acid can be used. Suitable comonomers include, in particular, monoethylene-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, as well as their anhydrides, such as maleic anhydride. Comonomers with sulfonic acid groups, such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, and vinylsulfonic acid, are also suitable. Hydrophobic comonomers are also suitable, such as isobutene, diisobutene, styrene, and alpha-olefins with 10 or more carbon atoms. Hydrophilic monomers with hydroxyl groups or alkylene oxide groups can also be used as comonomers.

[0097] Examples include allyl alcohol and isoprenol, as well as their alkoxylates and methoxypolyethylene glycol (meth)acrylate. Furthermore, graft polymers based on degraded starch and the aforementioned monomers, such as (meth)acrylic acid, maleic acid, fumaric acid, and 2-acrylamido-2-methylpropanesulfonic acid, can be used as cobuilders.

[0098] Since such components, unlike the graft polymers described above according to (b), are generally not readily biodegradable, it is a preferred embodiment of the invention that the polymers mentioned in the preceding section, in particular homopolymers and copolymers of acrylic acid or methacrylic acid, which preferably have a weight-average molar mass of 2000 to 50,000 g / mol, are not included in the formulations used according to the invention.

[0099] The cleaning agent formulations considered here may contain one or more surfactants selected from the group consisting of anionic, nonionic, cationic, zwitterionic, and amphoteric surfactants. Combinations of the aforementioned types of surfactants are also conceivable.

[0100] Preferred dishwashing detergent formulations are characterized in that the composition contains 1.0 to 6 wt.%, preferably 1.2 to 5.0 wt.%, based on the weight of the total composition, of non-ionic surfactants.

[0101] All nonionic surfactants known to those skilled in the art can be used. Preferably, weakly foaming nonionic surfactants are used, in particular alkoxylated, and especially ethoxylated, weakly foaming nonionic surfactants such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, or amine oxides. Particularly preferred nonionic surfactants are described in more detail below.

[0102] Preferred alcohol ethoxylates have a restricted homolog distribution (Narrow Range Ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.

[0103] Ethoxylated nonionic surfactants are particularly preferred, which are obtained from C6-20 monohydroxyalkanols or C6-20 alkylphenols or C16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol, and particularly more than 20 mol of ethylene oxide per mol of alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C16-20 alcohol), preferably from a C18 alcohol, and at least 12 mol, preferably at least 15 mol, and particularly at least 20 mol of ethylene oxide. The so-called "narrow-range ethoxylates" are particularly preferred.

[0104] Preferred surfactants come from the group of alkoxylated non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.

[0105] Within the scope of the present invention, low-foaming nonionic surfactants having alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred. Among these, surfactants with EO-AO-EO-AO blocks are preferred, wherein one to ten EO groups or AO groups are linked together before one block of the other group follows. Nonionic surfactants of the general formula are used in this context. Preferred are in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C6-24 alkyl or -alkenyl group; each R2 and R3 group is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2; and the indices w, x, y and z independently represent integers from 1 to 6.

[0106] Preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R1-OH and ethylene or alkylene oxide by known methods. The functional group R1 in the above formula can vary depending on the origin of the alcohol. When native sources are used, the functional group R1 has an even number of carbon atoms and is generally unbranched, with linear functional groups from native alcohols with 12 to 18 carbon atoms, such as coconut, palm, tallow, or oleyl alcohol, being preferred. Some examples of alcohols available from synthetic sources are the Guerbet alcohols or functional groups that are methyl-branched or linear and methyl-branched at the 2-position, as are commonly found in functional groups of oxo alcohols.Regardless of the type of alcohol used to produce the non-ionic surfactants contained in the agents, non-ionic surfactants are preferred in which R 1< represents a functional alkyl group with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15, especially 9 to 11, carbon atoms in the formula above.

[0107] Besides propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit, which alternates with the ethylene oxide unit in the preferred nonionic surfactants. Other alkylene oxides, in which R2< and R3< are selected independently, are also suitable.

[0108] -CH2CH2-CH3 and -CH(CH3)2 are also suitable. Preferably, nonionic surfactants of the above formula are used, in which R2< and R3< represent a functional group -CH3; w and x independently represent values ​​of 3 or 4; and y and z independently represent values ​​of 1 or 2.

[0109] Other preferably used non-ionic surfactants of the solid phase are non-ionic surfactants of the general formula R 1< O(AlkO)xM(OAlk)yOR , 2<

[0110] in which R 1< and R 2< independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl function with 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl function with 2 to 4 carbon atoms; x and y independently represent values ​​between 1 and 70; and M represents an alkyl function from the group CH2, CHR 3< , CR R 34< , CH2CHR 3< and CHR 3< CHR 4< , R 3< and R 4< , which independently represent a branched or unbranched, saturated or unsaturated alkyl function with 1 to 18 carbon atoms.

[0111] In this case, non-ionic surfactants of the general formula R 1< -CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)y-CH2CH(OH)-R , 2< are preferred, in which R, R 1< and R 2< independently represent a functional alkyl group or a functional alkenyl group with 6 to 22 carbon atoms; x and y independently represent values ​​between 1 and 40.

[0112] In this case, compounds of the general formula R< 1< -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH ) O-CH 2y2 CH(OH)-R , 2< are particularly preferred, where R represents a linear, saturated alkyl group with 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently represent values ​​of 20 to 30. Such compounds can be obtained, for example, by reacting alkyldiols HO-CHR-CH2- OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH groups to form a dihydroxy ether.

[0113] In this case, preferred nonionic surfactants are those of the general formula R 1< - CH(OH)CH2O-(AO)w- (AO)x-(A "O)y-(A‴O)zR 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or poly-unsaturated functional C6-24 alkyl or -alkenyl group; R 2< represents hydrogen or a linear or branched functional hydrocarbon group with 2 to 26 carbon atoms; A, A', A" and A‴ independently represent a functional group from the group -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3); w, x, y and z represent values ​​between 0.5 and 120, where x, y and / or z can also be 0.

[0114] Surprisingly, the addition of the above-mentioned non-ionic surfactants of the general formula R 1< - CH(OH)CH2O-(AO)w- (A'O)x-(A "O)y-(A‴O)zR 2< , hereinafter also referred to as "hydroxy mixed ethers", can significantly improve the cleaning performance of preparations used according to the invention, both in comparison to surfactant-free systems and in comparison to systems with alternative non-ionic surfactants, e.g. from the group of polyalkoxylated fatty alcohols.

[0115] By using these non-ionic surfactants, which have one or more free hydroxyl groups on one or both terminal alkyl functional groups, the stability of the enzymes contained in the cleaning preparations used according to the invention can be significantly improved.

[0116] In particular, end-capped poly(oxyalkylated) non-ionic surfactants corresponding to the following formula are preferred, , in addition to a functional group R 1< , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functions with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, also has a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon function R 2< with 1 to 30 carbon atoms, wherein n represents values ​​between 1 and 90, preferably values ​​between 10 and 80 and in particular values ​​between 20 and 60.

[0117] Surfactants of the above formula are particularly preferred, where R 1< represents C7 to C13, n represents an integer natural number from 16 to 28 and R 2< represents C8 to C12.

[0118] Particularly preferred are surfactants of the formula R1< O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2< , where R1< represents a linear or branched aliphatic hydrocarbon function with 4 to 18 carbon atoms or mixtures thereof, R2< represents a linear or branched hydrocarbon function with 2 to 26 carbon atoms or mixtures thereof, x represents values ​​between 0.5 and 1.5, and y represents a value of at least 15. This group of nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO)1-(EO)15-40-2-hydroxyalkyl ethers, in particular the C8-10 fatty alcohol (PO)1-(EO)22-2-hydroxydecyl ethers.

[0119] In particular, the end-capped poly(oxyalkylated) non-ionic surfactants of the formula R 1< O[CH2CH2O]x[CH2CH(R 3< )O]yCH2CH(OH)R 2< are preferred, in which R 1< and R 2< independently represent a linear or branched, saturated or monounsaturated or polyunsaturated hydrocarbon function with 2 to 26 carbon atoms, R 3< is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2, but preferably stands for -CH3, and x and y independently represent values ​​between 1 and 32, wherein non-ionic surfactants with R 3< = -CH3 and with values ​​for x from 15 to 32 and for y from 0.5 and 1.5 are particularly preferred.

[0120] Other preferably usable non-ionic surfactants are the end-capped poly(oxyalkylated) non-ionic surfactants of the formula R 1< O[CH2CH(R 3< )O]x[CH2]kCH(OH)[CH2]jOR 2< , in which R 1< and R 2< represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups with 1 to 30 carbon atoms, R 3< represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl functional group, x represents values ​​between 1 and 30 and k and j represent values ​​between 1 and 12, preferably between 1 and 5. If the value x > 2, then each R 3< in the above formula R 1< O[CH2CH(R 3< )O]x[CH2]kCH(OH)[CH2]jOR 2< can be different.R1< and R2< are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic functional hydrocarbon groups with 6 to 22 carbon atoms, with functional groups having 8 to 18 carbon atoms being particularly preferred. For functional group R3<, H, -CH3, or -CH2CH3 are particularly preferred. Particularly preferred values ​​for x are in the range of 1 to 20, especially from 6 to 15.

[0121] As described above, each R3< in the formula above can be different if x > 2. In this way, the alkylene oxide unit in square brackets can be varied. For example, if x represents 3, the functional group R3< can be chosen to form ethylene oxide (R3<= H) or propylene oxide (R3<= CH3) units, which can be linked together in any order, such as (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO), and (PO)(PO)(PO). The value 3 for x was chosen here as an example and can certainly be larger, with the range of variation increasing with the size of the values ​​for x, allowing, for example, a large number of (EO) groups to be combined with a small number of (PO) groups, or vice versa.

[0122] Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values ​​of k = 1 and j = 1, and therefore the previous formula simplifies to R1O[CH2CH(R3)O]XCH2CH(OH)CH2OR2. In the latter formula, R1, R2, and R3 are as defined above, and x represents numbers from 1 to 30, preferably from 1 to 20, and particularly from 6 to 18. Surfactants in which the functional groups R1 and R2 have 9 to 14 carbon atoms, R3 represents hydrogen, and x takes on values ​​from 6 to 15 are particularly preferred. Finally, the nonionic surfactants of the general formula R1-CH(OH)CH2O-(AO)wR2 have proven to be particularly effective, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated functional C6-24 alkyl or alkenyl group; R 2< represents a linear or branched functional hydrocarbon group with 2 to 26 carbon atoms; A represents a functional group from the group CH2CH2, CH2CH2CH2, CH2CH(CH3), preferably CH2CH2, and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 20 to 40.

[0123] Examples of these non-ionic surfactants include C4-22 fatty alcohol (EO)10-80-2 hydroxyalkyl ethers, in particular C8-12 fatty alcohol (EO)22-2 hydroxydecyl ethers and C4-22 fatty alcohol (EO)40-80-2 hydroxyalkyl ethers.

[0124] In various embodiments, the non-ionic surfactant is selected from non-ionic surfactants of the general formula R 1< -O(CH2CH2O)xCR R 34< (OCH2CH2)yO-R 2< , in which R 1< and R 2< independently represent an alkyl functional group or alkenyl functional group with 4 to 22 carbon atoms; R 3< and R 4< independently represent H or an alkyl functional group or alkenyl functional group with 1 to 18 carbon atoms and x and y independently represent values ​​between 1 and 40.

[0125] In particular, compounds of the general formula R 1< -O(CH2CH2O)xCR R 34< (OCH2CH2)yO-R 2< are preferred, in which R 3< and R 4< stand for H and the indices x and y independently take values ​​from 1 to 40, preferably from 1 to 15.

[0126] In particular, compounds of the general formula R 1< -O(CH2CH2O)xCR R 34< (OCH2CH2)yO-R 2< are preferred, wherein the functional groups R 1< and R 2< independently represent saturated alkyl functional groups with 4 to 14 carbon atoms and the indices x and y independently take values ​​of 1 to 15 and in particular of 1 to 12.

[0127] Furthermore, compounds of the general formula R 1< -O(CH2CH2O)xCR R 34< (OCH2CH2)yO-R 2< are preferred, in which one of the functional groups R 1< and R 2< is branched.

[0128] Compounds of the general formula R 1< -O(CH2CH2O)xCR R 34< (OCH2CH2)yO-R 2< are particularly preferred, where the indices x and y independently take values ​​from 8 to 12.

[0129] The specified carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages, which may be whole numbers or fractions for a given product. Due to the manufacturing processes, commercial products of the above-mentioned formulas generally do not consist of a single component but rather of mixtures. Therefore, average values ​​and resulting fractions may occur for both the carbon chain lengths and the degrees of ethoxylation and alkoxylation.

[0130] Of course, the above-mentioned non-ionic surfactants can be used not only as single substances, but also as surfactant mixtures of two, three, four or more surfactants.

[0131] Nonionic surfactants with a melting point above room temperature are particularly preferred. Nonionic surfactants with a melting point above 20 °C, preferably above 25 °C, particularly preferably between 25 and 60 °C, and especially between 26.6 and 43.3 °C are particularly preferred.

[0132] The nonionic surfactant, which is solid at room temperature, preferably has propylene oxide (PO) units in the molecule. Preferably, such PO units constitute up to 25 wt.%, particularly preferably up to 20 wt.%, and especially up to 15 wt.% of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably constitutes more than 30 wt.%, particularly preferably more than 50 wt.%, and especially more than 70 wt.% of the total molar mass of such nonionic surfactants. Preferred compositions are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule constitute up to 25 wt.%, preferably up to 20 wt.%, and especially up to 15 wt.%.-% of the total molar mass of the nonionic surfactant.

[0133] Further additives that can be used in connection with the dishwashing detergent formulations used according to the invention include, for example, anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, antifoaming agents, dyes, fragrances, fillers, solubilizers, or water. In addition to the ammonium or alkali carbonates, ammonium or alkali hydrogen carbonates, and ammonium or alkali sesquicarbonates already mentioned in connection with the builders, ammonium or alkali hydroxides, as well as mixtures of the aforementioned substances, can also be used as alkali carriers.

[0134] To prevent glass corrosion, which manifests as cloudiness, iridescence, streaks, and lines on the glass, glass corrosion inhibitors are preferably used. Preferred glass corrosion inhibitors include, for example, magnesium, zinc, and bismuth salts and complexes, as well as polyethyleneimine.

[0135] Corrosion inhibitors that can be used include, among others, silver preservatives from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, provided they are environmentally compatible.

[0136] The dishwashing detergent formulations used according to the invention can contain 0.001 to 5 wt% enzymes. Surprisingly, it was found that the enzyme activity, in particular the activity of the amylase(s) and / or protease(s), is significantly enhanced by the polymer combination (a), resulting in improved cleaning performance on enzyme-sensitive soils.

[0137] Dishwashing detergents are often enriched with enzymes to enhance cleaning performance or to maintain the same level of cleaning performance under milder conditions (e.g., at lower temperatures). The enzymes can be used in free form, chemically or physically immobilized on a carrier, or encapsulated.

[0138] The cleaning agents according to the invention preferably contain enzymes in total amounts of 1 x 10⁻⁶ wt% to 5 wt%, based on active protein. The protein concentration can be determined using known methods, e.g., the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method (Gornall et al., J. Biol. Chem. 177 (1948): 751-766). The determination of the active protein concentration can be carried out by titration of the active sites using a suitable irreversible inhibitor and determination of the residual activity (cf. Bender et al., J. Am. Chem. Soc. 88, 24 (1966): 5890-5913).

[0139] Among the proteases, those of the subtilisin type are preferred. Examples include the subtilisins BPN' and Carlsberg, as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, the subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases TW3 and TW7, which belong to the subtilases but no longer to the subtilisins in the strict sense.

[0140] Methods for determining protease activity are familiar to those skilled in the art in enzyme technology and are routinely used by them. For example, such methods are disclosed in Surfactants, Volume 7 (1970), pp. 125-132. Alternatively, the protease activity can be determined via the release of the chromophore para-nitroaniline (pNA) from the substrate suc-L-Ala-L-Ala-L-Pro-L-Phe-p-nitroanilide (AAPF). The protease cleaves the substrate and releases pNA. The release of pNA causes an increase in absorbance at 410 nm, the time course of which is a measure of the enzymatic activity (see Del Mar et al., 1979). The measurement is performed at a temperature of 25°C, pH 8.6, and a wavelength of 410 nm. The measurement time is 5 minutes and the measurement interval is 20 to 60 seconds. Protease activity is usually expressed in protease units (PE). Suitable protease activities are, for example, 2.25, 5, or 10 PE per ml of wash solution.However, the protease activity is not zero.

[0141] An alternative test for determining the proteolytic activity of the proteases according to the invention is an optical measurement method, preferably a photometric method. The suitable test comprises the protease-dependent cleavage of the substrate protein casein. This is cleaved by the protease into a multitude of smaller subproducts. The totality of these subproducts exhibits increased absorption at 290 nm compared to uncleaved casein, whereby this increased absorption can be determined using a photometer, and thus a conclusion can be drawn about the enzymatic activity of the protease.

[0142] Examples of amylases that can be used according to the invention are α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as further developments of the aforementioned amylases that have been improved for use in detergents. Of particular note in this context are the α-amylases from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

[0143] Cleaning-active proteases and amylases are generally not supplied as pure proteins, but rather as stabilized preparations suitable for storage and transport. These finished products include, for example, solid preparations obtained by granulation, extrusion, or freeze-drying, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously maximally concentrated, with low water content, and / or supplemented with stabilizers or other excipients.

[0144] Alternatively, the enzymes can also be encapsulated, e.g., by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, e.g., those in which the enzymes are enclosed in a solid gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. In the case of coatings, other active ingredients such as stabilizers, emulsifiers, pigments, or dyes can also be applied. Such capsules are applied using methods known per se, for example, by shake or roller granulation or by fluid bed granulation. Such granules are advantageously low in dust, e.g., through the use of polymeric film formers, and are storage-stable due to the coating.

[0145] As can be seen from the preceding explanations, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40 wt.%, preferably between 2 and 30 wt.%, and particularly preferably between 3 and 25 wt.% of the enzyme protein. In particular, cleaning agents are preferred which contain, based on their total weight, 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and especially 0.5 to 8 wt.% of the respective enzyme preparations.

[0146] If the dishwashing detergent formulations contain enzymes, they preferably contain them in amounts of 0.001 to 3.0% of the active enzyme protein, based on the weight of the total composition. The percentage of enzymes is calculated based on the mass of the active enzyme protein per unit weight of the total composition.

[0147] In a preferred embodiment, the dishwashing detergent formulation is characterized in that the composition comprises amylases in an amount of 0.05 to 20 mg of active enzyme protein per gram of the total composition, preferably 0.07 to 10 mg of active enzyme protein per gram of the total composition, most preferably 0.10 to 2 mg of active enzyme protein per gram of the total composition.

[0148] In a preferred embodiment, the dishwashing detergent formulation is further characterized in that the composition comprises proteases in an amount of 0.1 to 50 mg of active enzyme protein per gram of the total composition, preferably 0.2 to 25 mg of active enzyme protein per gram of the total composition, or 0.5 to 10 mg of active enzyme protein per gram of the total composition.

[0149] According to the invention, at least one amylase and at least one protease are preferably used.

[0150] The formulations according to the invention may contain one or more enzyme stabilizers. Enzyme stabilizers serve to protect enzymes – especially during storage – from damage such as inactivation, denaturation, or decomposition, e.g., by physical influences, oxidation, or proteolytic cleavage.

[0151] Examples of enzyme stabilizers include reversible protease inhibitors, such as benzamidine hydrochloride, borax, boric acid, boronic acids, or their salts or esters, including in particular derivatives with aromatic groups, e.g., ortho-, meta-, or para-substituted phenylboronic acids, especially 4-formylphenylboronic acid, or the salts or esters of the aforementioned compounds. Peptide aldehydes, i.e., oligopeptides with a reduced carbon terminus, especially those consisting of 2 to 50 monomers, are also used for this purpose. Peptide reversible protease inhibitors include, among others, ovomucoid and leupeptin. Specific reversible peptide inhibitors for the protease subtilisin, as well as fusion proteins of proteases and specific peptide inhibitors, are also suitable for this purpose.Other examples of enzyme stabilizers include amino alcohols such as mono-, di-, triethanolamine and triethanolamine and their mixtures, aliphatic mono- and dicarboxylic acids up to C12 carboxylic acids, such as succinic acid. Terminally capped fatty acid amidoalkoxylates are also suitable as enzyme stabilizers.

[0152] Other examples of enzyme stabilizers include sodium sulfite, reducing sugars, and potassium sulfate. Sorbitol is another example of a suitable enzyme stabilizer.

[0153] Organic solvents may also be present, but are preferably limited to an amount of up to 30% by weight of the composition. Particularly preferred organic solvents are propanediol, glycerol, and / or sorbitol. These amounts of organic solvents contribute to the free-flowing properties and the stabilization of the active ingredients.

[0154] In a preferred embodiment of the present invention, the dishwashing detergent composition used according to the invention contains one or more organic solvents selected from the group consisting of sorbitol, glycerol, and / or propanediol. Preferably, the composition contains 1 to 25 wt.%, more preferably 2 to 12 wt.% of the total composition from the group consisting of sorbitol, glycerol, and / or propanediol.

[0155] The dishwashing detergent formulation used according to the invention is preferably characterized in that the composition has a pH value of 7.0 to 11.5 at 20 °C. The pH value is measured in the undiluted product itself. A suitable measuring device is, for example, a conventional pH electrode.

[0156] According to a preferred embodiment of the present invention, the composition used comprises (i) 1 to 4 wt% of a) at least one polyaspartic acid or modified polyaspartic acid or its salts, wherein the modified polyaspartic acid is obtained by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably from 11:1 to 8:1, particularly preferably 11:1 to 9:1; (ii) 5 - 20 wt.-% citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iii) 0.2 - 0.8 wt% xanthan gum; (iv) at least 20 wt% water; (v) 1 - 5 wt% non-ionic surfactants and (vi) 0.001 - 3 wt% enzymes.

[0157] Preferably, the composition has a pH value of 7.0 to 8.5, preferably 7.5 to 8.0 at 20 °C.

[0158] The stability of the enzymes is increased by the comparatively low pH value. These formulations are remarkably well-suited for cleaning delicate dishes without damaging glass or decorations on glass or porcelain.

[0159] These compositions can also be used alone or as the enzyme-containing component (A) of a multi-component system. Preferably, composition A has a pH of 7.0 to 8.5, more preferably 7.5 to 8.0 at 20 °C. The stability of the enzyme is increased by the pH value.

[0160] Another object of the present invention is the use of a phosphate-free, liquid dishwashing detergent formulation at 20 °C, which is free of bleaching agents, comprising at least two different compositions, one of which is composition A, comprising, in each case based on the weight of composition A: (i) 1-5 wt% of (a) at least one of polyaspartic acid or modified polyaspartic acid or its salts, wherein the modified polyaspartic acid is obtained by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1; (ii) 3 to 25 wt.(iii) Complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), ethyleneamine diacetic acid (EDDS) and / or their salts as complexing agents; (iv) 0.15 to 6 wt thickening agents, preferably selected from polysaccharides, in particular xanthan gum; (iv) at least 20 wt% water and (v) optionally 4 to 15 wt% builders and / or cobuilders; (vi) optionally 0.5 to 8 wt% non-ionic surfactants; (vii) 0.001 to 3 wt% enzymes; (viii) optionally 2 to 30 wt% organic solvents. for improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

[0161] The above information regarding the composition refers, in this particular embodiment, to composition A. Accordingly, the above information regarding the overall composition always refers to overall composition A.

[0162] A preferred embodiment of the invention consists in the cleaning composition being characterized by comprising two different liquid compositions A and B, wherein composition A contains at least one enzyme and composition B is preferably enzyme-free. According to this embodiment of the present invention, composition A and composition B are separate from each other. Within the scope of the present invention, this means that composition A and B differ in their formulation and are also spatially separated from each other. It is particularly preferred if formulations A and B are spatially separated from each other but packaged together in a single packaging unit.

[0163] In preferred composition A, at least one enzyme is contained, and composition B is free of enzymes.

[0164] The term "spatially separated," as used here in reference to compositions A and B of the cleaning agent used according to the invention, means that the individual components of composition A cannot come into contact with the components of composition B. Typically, the cleaning agent according to the invention can be provided for this purpose in the form of a multi-chamber package, such as a bottle, a tube, or a pouch, in particular a two-chamber bottle or pouch, wherein compositions A and B are arranged separately from each other in separate, distinct chambers.

[0165] According to a preferred use of the dishwashing formulation according to the invention, the liquid composition A and / or B contains 30 to 80 wt.%, preferably 40 to 75 wt.%, in particular 45 to 70 wt.% water, based on the total weight of the respective composition A or B.

[0166] In a further embodiment of the present invention, it is preferred that the composition B comprises methylglycine diacetic acid (MGDA) and / or its salts as complexing agents, wherein the amount of methylglycine diacetic acid (MGDA) and its salts is preferably 4.5 to 25%, in particular 5 to 20% by weight, based on the weight of the total composition B.

[0167] In a particularly preferred embodiment, the thickener in composition B is xanthan gum, preferably contained in an amount of 0.2 to 0.8 wt.%, based on the total weight of composition B.

[0168] In a further embodiment, composition B contains a builder according to (x), preferably in an amount of 4 to 15% wt.%, particularly 7 to 10% wt.%, in each case based on the total weight of composition B. This builder is different from the complexing agents according to (ix) and is preferably selected from carbonates, bicarbonates, or mixtures thereof. These are preferably used in an amount of 4 to 15% wt.%. In particular, an alkali metal carbonate is preferably included in composition B in an amount of 5 to 12% wt.%, particularly preferably 7 to 10% wt.%, in each case based on the total weight of composition B.

[0169] According to a particularly preferred embodiment, the compositions A and B are present in a weight ratio of A to B of 2:1 to 1:2, preferably of 1.5:1 to 1:1.5, in particular of 1.2:1 to 1:1.2, most preferably of 1.15:1 to 1:15, or are used in the aforementioned weight ratio in a dishwashing process.

[0170] Composition B is preferably characterized in that it has a pH value of 9 to 11.5 at 20 °C. These compositions can be used alone or as alkaline compositions (B) of a multi-component system.

[0171] In preferred embodiments, the composition B contains 1 to 7 wt.%, preferably 2 to 5 wt.% phosphonates or their salts, preferably 1-hydroxyethane-1,1-diphosphonate (HEDP) or its salt, preferably its sodium salt, as a cobuilder.

[0172] In another embodiment, it is preferred that composition B contains less than 0.1 wt% phosphonates and their salts, preferably less than 0.01 wt% phosphorus-containing components.

[0173] A particularly preferred embodiment is characterized in that, in the use according to the invention, composition A, as described above, and composition B (alkali phase) each comprise: (ix) 3 to 30 wt% complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20 wt% builders and / or cobuilders not identical to the complexing agents according to (ix); (xi) 0.15 to 2 wt% thickeners, preferably selected from polysaccharides, in particular xanthan gum; (xii) 0.01 to 3 wt% anionic surfactant, preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates; and (xiii) at least 20 wt% water.

[0174] By spatially separating individual components of the agent, it is possible, on the one hand, to separate incompatible ingredients from each other and, on the other hand, to provide several different components of the agent in combination, which can be used / released at different times when applying the cleaning agent used according to the invention.

[0175] In another aspect, the invention relates to the use of a cleaning agent for machine dishwashing, comprising at least two compositions A and B which are liquid at 20 °C, wherein composition A (enzyme phase) comprises: (i) 1–5 wt% of the total composition A of (a) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound other than aspartic acid, and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably 11:1 to 8:1, particularly preferably 11:1 to 9:1; (ii) 3 to 30 wt.(iii) 0.1 to 2 wt% of total composition A of complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iv) 0.5 to 8 wt% of total composition A of thickening agents, preferably selected from polysaccharides, in particular xanthan gum; (iv) 0.5 to 8 wt% of total composition A of nonionic surfactants; (v) 0.001 to 3 wt% of total composition A of enzymes; (vi) 0 to 15 wt% of total composition A of builders and / or co-builders other than (ii); (vii) 0 to 30 wt% of total composition A of organic solvents; and (viii) at least 20 wt% water AND .

[0176] Where composition B (alkaline phase), in each case based on the total weight of composition B, comprises: (ix) 3 to 30 wt% complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20 wt% builders and / or cobuilders not identical to the complexing agents according to (ix); (xi) 0.15 to 2 wt% thickeners, preferably selected from polysaccharides, in particular xanthan gum; and (xiii) at least 20 wt% water. for improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

[0177] In another aspect, the invention relates to the use of a cleaning agent for machine dishwashing, comprising at least two compositions A and B which are liquid at 20 °C, wherein composition A (enzyme phase) comprises, in each case, the following proportions based on the total weight of composition A: (i) 1–5 wt% of the total composition A of (a) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound other than aspartic acid, and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably from 11:1 to 8:1, particularly preferably from 11:1 to 9:1; (ii) 3 to 30 wt.(iii) 0.1 to 2 wt% of total composition A of complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iv) 0.5 to 8 wt% of total composition A of thickening agents, preferably selected from polysaccharides, in particular xanthan gum; (iv) 0.5 to 8 wt% of total composition A of nonionic surfactants; (v) 0.001 to 3 wt% of total composition A of enzymes; (vi) 0 to 15 wt% of total composition A of builders and / or co-builders other than (ii); (vii) 0 to 30 wt% of total composition A of organic solvents; and (viii) at least 20 wt% water AND .

[0178] Where composition B (alkaline phase), in each case based on the total weight of composition B, comprises: (ix) 3 to 30 wt% complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20 wt% builders and / or cobuilders not identical to the complexing agents according to (ix); (xi) 0.15 to 2 wt% thickeners, preferably selected from polysaccharides, in particular xanthan gum; (xii) 0.01 to 3 wt% anionic surfactant, preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates; and (xiii) at least 20 wt% water. for improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

[0179] It is particularly preferable if the composition B (alkali phase), in each case based on the weight of composition B, comprises: (ix) 3 to 30 wt% complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20 wt% builders and / or cobuilders not identical to the complexing agents according to (ix); (xi) 0.15 to 2 wt% thickeners, preferably selected from polysaccharides, in particular xanthan gum; (xii) 0.01 to 3 wt% anionic surfactant, preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates; and (xiii) at least 20 wt% water.

[0180] The dishwashing detergent formulation preferably contains an anionic surfactant as component (xii) in an amount of 0.01 to 3 wt.% of the total composition B. The anionic surfactant is preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates, and alkylbenzenesulfonates. Even more preferably, the anionic surfactant according to component xii) is selected from the group consisting of alkyl sulfonates with ≥ C14, alkyl sulfates with ≥ C14, and alkylbenzenesulfonates with ≥ C12. It is further preferred that the anionic surfactant according to xii) is selected from the group consisting of alkyl sulfates with a linear or branched, preferably linear, alkyl group containing at least 14, preferably 16, carbon atoms in the alkyl chain.

[0181] Linear alkyl sulfates or alkyl sulfonates with at least 14 carbon atoms in the alkyl group, or alkyl benzyl sulfonates with at least 12, preferably 14, carbon atoms in the alkyl group, are preferred. Linear alkyl sulfates with at least 14, preferably at least 16, carbon atoms in the alkyl group are particularly preferred.

[0182] In a preferred embodiment, the anionic surfactant according to component xii) is present in the form of individual detergent particles, which preferably have an average particle size of 0.1 to 4 mm, more preferably 0.25 to 3 mm, and in particular 0.5 to 2 mm, as determined by a sieve column. Each detergent particle preferably contains at least 50 wt.% of the surfactant, based on the weight of the particle.

[0183] In a highly preferred embodiment, the detergent particles are contained in composition B in an amount of 0.05 to 5 wt.%, preferably 0.1 to 3.5 wt.%, and particularly 0.2 to 2 wt.%, based on the total weight of the cleaning composition B. Linear alkyl sulfate surfactant particles (such as Lanette® < E ex BASF) are particularly preferred in an amount of 0.2 to 2 wt.%, based on the total weight of the cleaning composition B.

[0184] The detergent particles are evenly distributed in composition B and float in the thickened mixture. Xanthan gum stabilizes the particles in the gel formulation without causing separation or sedimentation. Therefore, the mixture pours evenly from the packaging with the particles uniformly distributed. Even after four weeks of storage at 40 °C, the particles remain evenly distributed in composition B, and no sedimentation has occurred.

[0185] Surprisingly, it was found that the cleaning agent particles in composition B are stably dispersed within composition B. The resulting cleaning composition is visually pleasing, pours evenly from a packaging device into the dosing chamber of an automatic dishwasher, and exhibits better cleaning performance than compositions without anionic detergent particles or compositions not manufactured in two separate compositions A and B.

[0186] It is particularly preferred if the composition B has a rheological yield strength of at least 0.1 Pascal (measured with a TA Instruments Discovery HR 2 rheometer), preferably so that the particles can be well stabilized and do not sink during storage.

[0187] In a further aspect, the present invention relates to the use of a cleaning composition, as described above, for cleaning dishes of stubborn carbohydrate-containing soiling, preferably baked-on and / or burnt-on carbohydrate-containing soiling, particularly protein- and carbohydrate-containing soiling, and especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soiling. The compositions are preferably used in dishwashers and / or automatic dishwashers. For the purposes of the present invention, "dishes" means plates, cups, cutlery, glasses, storage containers, cooking utensils (cookware), and the like.

[0188] The dispensing or introduction of the agent into the interior of the dishwasher can be done manually; however, it is preferably dispensed into the interior of the dishwasher by means of the dosing chamber. In various embodiments of the disclosure, the (washing) temperature in such dishwashing methods is preferably 50°C or less, particularly preferably 45°C or less, and even more preferably 40°C or less.

[0189] All embodiments disclosed herein with respect to the liquid compositions apply similarly to the processes and uses of the invention and vice versa.

[0190] Preferred embodiments of the present invention are described in more detail by the following points. 1. Use of a phosphate-free, liquid dishwashing detergent formulation at 20 °C, which is free of bleaching agents, comprising, in each case based on the weight of the total composition, (i) 0.5 to 5 wt.-%, of (a) at least one of polyaspartic acid or modified polyaspartic acid or their salts, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1; (ii) 3 to 25 wt.-% Complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), ethylenediamine diacetic acid (EDDS) and / or their salts as complexing agents; (iii) 0.1 to 6 wt.% thickening agent; (iv) at least 20 wt.% water and (v) optionally 4 to 15 wt.% builder and / or cobuilder; (vi) optionally 0.5 to 8 wt.% non-ionic surfactants; (vii) 0.001 to 3 wt.% enzymes; (viii) optionally 2 to 30 wt.% organic solvents to improve cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils. 2. Use of a dishwashing detergent formulation according to point 1, characterized in that the weight ratio of (a) : (b) is from 11:1 to 8:1. 3.1. Use of a dishwashing detergent formulation according to one of points 1 or 2, characterized in that the weight ratio of (a) : (b) is from 11:1 to 9:1. 2. Use of a dishwashing detergent formulation according to one of points 1 to 3, characterized in that the amount of the component according to (i) is 1.0% to 4.5%, preferably 1.2% to 4.0% by weight, based on the weight of the total composition. 3. Use of a dishwashing detergent formulation according to one of points 1 to 4, characterized in that the composition contains methylglycine diacetic acid (MGDA) and / or its salts as complexing agents. 4. Use of a dishwashing detergent formulation according to one of points 1 to 5, characterized in that the amount of methylglycine diacetic acid (MGDA) and its salts is 4.5% to 20% by weight, in particular 5% to 20% by weight of the total composition. 5.8. Use of a dishwashing detergent formulation according to any one of points 1 to 6, characterized in that the thickening agent is selected from polysaccharides, in particular xanthan gum, urea derivatives, and cross-linked polyacrylic acids. 9. Use of a dishwashing detergent formulation according to any one of points 1 to 7, characterized in that the thickening agent is xanthan gum, preferably used in an amount of 0.2 to 0.8 wt.% of the total composition. 10. Use of a dishwashing detergent formulation according to any one of points 1 to 8, which contains polyaspartic acid as a homopolymer in component i) a). 11. Use of a dishwashing detergent formulation according to any one of points 1 to 9, which contains a modified polyaspartic acid or a salt thereof, obtainable by polycondensation of (a1) comprising 80 to 95 mol% aspartic acid and (a2) comprising 5 to 20 mol% of at least one carboxyl-containing compound other than aspartic acid. 11.Use of a dishwashing detergent formulation according to point 10, wherein the at least one carboxyl-containing compound (a2) is selected from the group consisting of 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, and glutamic acid. 12. Use of a dishwashing detergent formulation according to any one of points 1 to 11, wherein the monomer (b3) is at least one compound of the general formula (I). wherein the variables are defined as follows: Z is O or NR 1< , R 1< is selected from methyl and hydrogen, A1 is selected from C 2-C 4 alkylenes, R 2< are the same or different and selected from C 1-C 4 alkyl, X -< is selected from halide, mono-C1-C4 alkyl sulfate and sulfate. 13. Use of a dishwashing detergent formulation according to point 12, wherein ZO is . 14. Use of a dishwashing detergent formulation according to any one of points 11 to 12, wherein R 2< is identical and methyl, A1 is CH 2 CH 2 and X -< is chloride. 15. Use of a dishwashing detergent formulation according to points 11 to 14, wherein the monomer (b3) is trimethylaminoethyl(meth)acrylatochloride or methacrylamidopropyltrimethylammonium chloride, preferably ω-trimethylaminoethyl(meth)acrylatochloride. 16. Use of a dishwashing detergent formulation according to one of points 1 to 15, characterized in that the composition contains a builder of 5 to 12 wt.%, preferably 7 to 10 wt.%.-% of the total composition, contains an alkali carbonate. 17. Use of a dishwashing detergent formulation according to any one of points 1 to 16, characterized in that the composition contains 1 to 7 wt.%, preferably 2 to 5 wt.% of the total composition as a cobuilder a phosphonate or its salts, preferably HEDP or its salts, in each case based on the weight of the total composition. 18. Use of a dishwashing detergent formulation according to any one of points 1 to 16, characterized in that the composition contains, in each case based on the weight of the total composition, less than 0.1 wt.%, preferably less than 0.01 wt.%, of phosphonates, preferably the composition contains less than 0.01 wt.% of phosphorus-containing compounds. 19. Use of a dishwashing detergent formulation according to any one of points 1 to 18, characterized in that the composition contains 1.0 to 6 wt.%, preferably 1.2 to 5.0 wt.-%, in each case based on the weight of the total composition, contains nonionic surfactants. 20. Use of a dishwashing detergent formulation according to any one of points 1 to 19, characterized in that the composition comprises amylases in an amount of 0.05 to 20 mg of active enzyme protein per gram of the total composition, preferably 0.07 to 10 mg of active enzyme protein per gram of the total composition, most preferably 0.10 to 2 mg of active enzyme protein per gram of the total composition. 21. Use of a dishwashing detergent formulation according to any one of points 1 to 20, characterized in that the composition comprises proteases in an amount of 0.1 to 50 mg of active enzyme protein per gram of the total composition, preferably 0.2 to 25 mg of active enzyme protein per gram of the total composition, 0.5 to 10 mg of active enzyme protein per gram of the total composition. 22.23. Use of a dishwashing detergent formulation according to any one of points 1 to 21, characterized in that the composition contains one or more organic solvents selected from the group consisting of sorbitol, glycerol, and / or propanediol. 24. Use of a dishwashing detergent formulation according to point 22, characterized in that the composition contains, in each case based on the weight of the total composition, 1 to 25 wt.%, preferably 2 to 12 wt.% of the total composition from the group consisting of sorbitol, glycerol, and / or propanediol. 25. Use of a dishwashing detergent formulation according to any one of points 1 to 23, characterized in that the composition has a pH of 7.0 to 11.5 at 20 °C. 26. Use of a dishwashing detergent formulation according to any one of points 1 to 24, characterized in that the composition comprises, in each case based on the weight of the total composition: (i) 1 to 4 wt.% of the total composition.-% of a) at least one of polyaspartic acid or modified polyaspartic acid or its salts, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably from 11:1 to 8:1, particularly preferably from 11:1 to 9:1; (ii) 5 - 20 wt.-% citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iii) 0.2 - 0.8 wt% xanthan gum; (iv) at least 20 wt% water; (v) 1 - 5 wt% non-ionic surfactants and (vi) 0.001 - 3 wt% enzymes. 26. Use of a phosphate-free, liquid dishwashing detergent formulation at 20 °C, which is free of bleaching agents, comprising at least two different compositions, wherein a composition A comprises, in each case based on the weight of composition A: (i) 1 - 5 wt%-%, of (a) at least one of polyaspartic acid or modified polyaspartic acid or its salts, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably from 11:1 to 8:1, particularly preferably from 11:1 to 9:1; (ii) 3 to 25 wt.(iii) Complexing agent selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), ethyleneamine diacetic acid (EDDS) and / or their salts as complexing agents; (iv) 0.15 to 6 wt thickening agent, preferably selected from polysaccharides, in particular xanthan gum; (iv) at least 20 wt% water and (v) optionally 4 to 15 wt% builder and / or cobuilder; (vi) optionally 1 to 8 wt% non-ionic surfactants; (vii) 0.001 to 3 wt% enzymes; (viii) optionally 2 to 30 wt% organic solvents to improve cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils. 27.Use of a phosphate-free, liquid dishwashing detergent formulation at 20 °C, which is free of bleaching agents, comprising at least two separate compositions, wherein composition A is a dishwashing detergent formulation according to points 1 to 26, for improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils. 28. Use of a dishwashing detergent formulation according to one of points 26 or 27, characterized in that composition B (alkali phase), in each case based on the weight of composition B, comprises: (ix) 3 to 30 wt.-% Complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20% wt% builders and / or cobuilders, which are not identical to the complexing agents according to (ix); (xi) 0.15 to 2% wt% thickeners, preferably selected from polysaccharides, in particular xanthan gum; and (xiii) at least 20% wt% water. 29. Use of a dishwashing formulation according to one of points 26 or 27, characterized in that the composition B (alkali phase), in each case based on the weight of composition B, comprises: (ix) 3 to 30% wt% complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20% wt% builders and / or cobuilders not identical to the complexing agents according to (ix); (xi) 0.15 to 2 wt%-% thickener, preferably selected from polysaccharides, in particular xanthan gum, (xii) 0.01 to 3 wt.% anionic surfactant, preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates; and (xiii) at least 20 wt.% water. 30. Use of a dishwashing formulation according to point 29, characterized in that the anionic surfactant according to xii) is selected from the group consisting of alkyl sulfonates with ≥ 14 carbon atoms in the alkyl chain, alkyl sulfates with ≥ 14 carbon atoms in the alkyl chain and alkylbenzenesulfonates with ≥ 12 carbon atoms. 31. Use of a dishwashing formulation according to one of points 29 or 30, characterized in that the anionic surfactant according to xii) is selected from the group consisting of alkyl sulfates having a linear or branched, preferably linear, alkyl group containing at least 14, preferably 16, carbon atoms in the alkyl chain. 32.Use of a dishwashing formulation according to any one of points 29 to 31, characterized in that the anionic surfactant according to xii) is present as distinct cleaning particles, preferably with an average particle size of 0.1 to 4 mm, in particular of 0.25 to 3 mm, most preferably of 0.5 to 2 mm, determined by a sieve column. 33. Use of a dishwashing formulation according to any one of points 29 to 32, characterized in that the cleaning particle is present in composition B in an amount of 0.05 to 5% by weight, preferably of 0.1 to 3.5% by weight, in particular of 0.15 to 2% by weight, in each case based on the total weight of composition B. 34. Use of a dishwashing formulation according to any one of points 29 to 33, characterized in that the cleaning particle contains at least 50% by weight of surfactant, based on the total weight of the particle. 35.36. Use of a dishwashing formulation according to any one of points 28 to 34, characterized in that composition B has a rheological yield strength of at least 0.1 Pascal. 36. Use of a dishwashing formulation according to any one of points 28 to 35, characterized in that the liquid compositions A and / or B contain 30 to 80 wt.%, preferably 40 to 75 wt.%, in particular 45 to 70 wt.% water, based on the total weight of the respective composition A or B. 37. Use of a dishwashing detergent formulation according to any one of points 28 to 36, characterized in that composition B has a pH of 9 to 11.5 at 20 °C. 38.Use of a dishwashing detergent formulation according to any one of points 28 to 37, characterized in that composition B comprises methylglycine diacetic acid (MGDA) and / or its salts as complexing agents, wherein the amount of methylglycine diacetic acid (MGDA) and its salts is preferably 4.5 to 25%, in particular 5 to 20% by weight, in each case based on the weight of the total composition B. 39. Use of a dishwashing detergent formulation according to any one of points 28 to 38, characterized in that the thickener is xanthan gum, preferably in an amount of 0.2 to 0.8% by weight, based on the total weight of composition B. 40. Use of a dishwashing detergent formulation according to any one of points 28 to 39, characterized in that composition B contains a builder according to (x), preferably in an amount of 4 to 15% by weight, in particular 7 to 10% by weight, in each case based on the total weight of composition B. 41.Use of a dishwashing detergent formulation according to any one of points 28 to 40, characterized in that composition B contains as a builder according to (x) carbonates, bicarbonates or mixtures thereof, preferably in an amount of 4 to 15% by weight, in particular an alkali metal carbonate preferably in an amount of 5 to 12% by weight, particularly preferably 7 to 10% by weight, in each case based on the total weight of composition B. 42. Use of a dishwashing detergent formulation according to any one of points 28 to 41, characterized in that composition B contains 1 to 7% by weight, preferably 2 to 5% by weight, phosphonates or their salts, preferably 1-hydroxyethane-1,1-diphosphonate (HEDP) or its salt as a cobuilder. 43. Use of a dishwashing detergent formulation according to any one of points 28 to 42, characterized in that composition B contains less than 0.1 wt% phosphonates and their salts, preferably less than 0.01 wt% phosphorus-containing components. 44.45. Use of a dishwashing detergent formulation according to any one of points 28 to 43, characterized in that compositions A and B are contained in different compartments of a packaging unit. 46. Use of a dishwashing detergent formulation according to any one of points 28 to 44, characterized in that compositions A and B are present in a weight ratio of A to B of 2:1 to 1:2, preferably of 1.5:1 to 1:1.5, particularly of 1.2:1 to 1:1.2, most preferably of 1.15:1 to 1:15. 47. Use of a dishwashing detergent formulation according to any one of points 1 to 45, comprising at least two compositions A and B which are liquid at 20 °C, wherein composition A (enzyme phase) comprises: (i) 1–5 wt.-% of the total composition A from (a) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound other than aspartic acid, and subsequent hydrolysis of the cocondensates upon addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably of 11:1 to 8:1, particularly preferably 11:1 to 9:1; (ii) 3 to 30 wt.(iii) % of total composition A of complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iii) 0.1 to 2 wt.% of total composition A of thickening agents, preferably selected from polysaccharides, in particular xanthan gum; (iv) 0.5 to 8 wt.% of total composition A of nonionic surfactants; (v) 0.001 to 3 wt.% of total composition A of enzymes; (vi) 0 to 15 wt.% of total composition A of builders and / or co-builders other than (ii); (vii) 0 to 30 wt.% of total composition A of organic solvents; and (viii) at least 20 wt.% of water. Wherein composition B (alkaline phase), in each case based on the total weight of composition B, comprises: (ix) 3 to 30 wt.% of total composition A.(x) Complexing agent selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20% wt% builder and / or cobuilder, which are not identical to the complexing agents according to (ix); (xi) 0.15 to 2% wt% thickener, preferably selected from polysaccharides, in particular xanthan gum; (xii) optionally 0.01 to 3% wt% anionic surfactant, preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates; and (xiii) at least 20% wt% water. For improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, especially protein- and carbohydrate-containing soils, particularly preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils. 47.A method for machine dishwashing, characterized in that a cleaning agent according to one of claims 1 to 45 is brought into contact with dishes that have stubborn carbohydrate-containing soiling, preferably baked-on and / or burnt-on carbohydrate-containing soiling, in particular protein- and carbohydrate-containing soiling, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soiling. Examples:

[0191] Exemplary compositions have been prepared, where the amounts of active ingredients in wt.% refer to the total weight of the composition, unless otherwise stated. Table 1: Single-phase cleaning agents ingredient Comparison example V1 E1 Xanthan gum 0.6 0.6 1-Hydroxyethane-1,1-di-phosphonate (HEDP), disodium salt 0.0 0.0 Acusol ®< 588 G (ex DOW Inc.) 0.0 0.0 Polyacrylate, homopolymer 4.0 0.0 Polyaspartic acid, homopolymer 0.0 2.0 Graft polymer, described in WO2019 / 211231 as polymer P2 0.0 0.2 MGDA, trisodium salt 6.00 6.00 Calcium chloride 0.3 0.3 Sodium carbonate 0.00 0.00 Cationic acrylate-based copolymer 0.67 0.0 Sodium citrate (dihydrate) 4.5 4.5 Low foaming non-ionic surfactant (hydroxy mixed ether) 2.00 2.00 Stainzyme ®< 12 L (amylase available from Novozymes) 1.7 1.7 Protease (specified as active enzyme protein in mg per 100g composition) 120 120 perfume 0.05 0.05 dye 0.005 0.005 preservatives 0.5 0.5 Formic acid To achieve the specified pH value To achieve the specified pH value Water Ad 100 Ad 100

[0192] The pH of the undiluted liquid phase was adjusted to 7.8 at 20 °C. Determination of cleaning performance:

[0193] Cleaning performance was determined according to IKW 2016 standards in a Miele GSL 2 dishwasher using program 45-8-55. The water hardness was 21 °dH. Ballast dirt according to IKW 2016 standards was used. 30 g each of the single-component formulations E1 and V1 were used as detergents. After each wash cycle, the dishes were visually inspected on a scale of 1-10. The higher the score, the better the cleaning performance. The results are shown in Table 2. Table 2: Results Crème Brûlée Example E1 6,4 Comparison example V1 5,4

[0194] It was observed that the compositions used according to the invention significantly improved the cleaning performance of Creme Brûlée (see Table 2) despite the absence of acrylic-based thickeners and high-acrylate active ingredients. Table 3: Two-phase compositions Enzyme phase (composition A) V2 E2 Ca chloride 0.27 0.27 Xanthan gum 0 0.45 Polyacrylate-based thickener 0.9 0.0 Polyaspartic acid, homopolymer (polymer a), wt% active substance) 0 3.9 Graft polymer as described in WO2019 / 211231 as polymer P2 (polymer b), wt% (active substance) 0 0.4 Sulfonic acid group-containing acrylate copolymer 4.8 0 Sodium citrate x 2H₂O 4.0 4.0 MGDA, trisodium salt 10 10 Citric acid (anhydrous) 2.8 2.8 Non-ionic surfactant 3.5 3.5 Protease (wt% active enzyme protein) 0.26 0.26 Stainzyme 12L (telqel), amylase preparation 1.6 1.6 Perfumes, preservatives, dyes, other additives 1.5 1.5 Water Add 100 Add 100

[0195] The pH of the undiluted liquid phase was adjusted to 7.8 at 20 °C. Alkali phase (composition B) V2 E2 Xanthan gum 0 0.375 Polyacrylate-based thickener 0.9 0 HEDP, sodium salt 4.5 4.5 KOH 5 5 MGDA, trisodium salt 10 10 Sodium citrate x 2H₂O 0 4.0 Lanette ®< E Granules ex BASF (anionic surfactant) 0.25 0.25 soda 9 9 Cationic acrylate-based polymer 0.2 0 Perfumes, preservatives, dyes, other additives 1.5 1.5 Water Add 100 Add 100

[0196] The pH of the undiluted liquid phase was adjusted to 8.5 at 20 °C.

[0197] The cleaning performance was determined in a dishwasher (Bosch SMS6ECW57E / 38 in the 65°C 1h program) according to IKW standards for the aforementioned two-phase compositions (Table 3). For this purpose, 16 g of the enzyme phase (E2 or V2) and 18 g of the alkaline phase (E2 or V2) were dosed into the cleaning cycle according to the two-component formulations E2 and V2, respectively. The results are shown in Table 4. Table 4: Results spaghetti Example E2 6,3 Comparison example V2 3,3

[0198] It was observed that the compositions used according to the invention significantly improved the cleaning performance of spaghetti (see Table 4) despite the absence of acrylic-based thickeners and high-acrylate active ingredients. Table 5: Other suitable single-phase compositions component E3 Xanthan gum 0.5 1-Hydroxy-1-phosphonoethyl)phosphonic acid (HEDP), sodium salt 0 Acrylate homopolymer 0 Acusol® < 588 G (formerly DOW Inc.) 0 Polyaspartic acid, homopolymer (polymer a) 2.0 Graft polymer as described in WO2019 / 211231 as polymer P2 (polymer b) 0.2 MGDA, trisodium salt 10.00 Calcium chloride 0.2 Citric acid anhydrous 2.6 Sodium citrate 7.00 Low-foaming non-ionic surfactant (hydroxy mixed ether) 2.00 Stainzyme® < 12 L (amylase available from Novozymes) 1.5 Protease (expressed as active enzyme protein in mg per 100 g composition) 150 perfume 0.05 dyeing 0.005 preservatives 0.5 NaOH Water Add 100 PH value 7.8

Claims

1. Use of a phosphate-free, liquid dishwashing detergent formulation at 20 °C, which is free of bleaching agents, comprising, in each case based on the weight of the total composition, (i) 0.5 to 5 wt.-%, of (a) at least one of polyaspartic acid or modified polyaspartic acid or their salts, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1; (ii) 3 to 25 wt.-% Complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), ethylenediamine diacetic acid (EDDS) and / or their salts as complexing agents; (iii) 0.1 to 6 wt.% thickening agent; (iv) at least 20 wt.% water and (v) optionally 4 to 15 wt.% builder and / or cobuilder; (vi) optionally 0.5 to 8 wt.% non-ionic surfactants; (vii) 0.001 to 3 wt.% enzymes; (viii) optionally 2 to 30 wt.% organic solvents to improve cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

2. Use of a dishwashing detergent formulation according to claim 1, characterized by the fact thatthe weight ratio of (a): (b) is from 11:1 to 8:1, preferably from 11:1 to 9:

1.

3. Use of a dishwashing detergent formulation according to one of claims 1 to 2, characterized by the fact that the amount of the component according to (i) shall be 1.0% to 4.5%, preferably 1.5% to 4.0% by weight, based on the total weight of the composition.

4. Use of a dishwashing detergent formulation according to any one of claims 1 to 3, characterized by the fact that the composition comprises methylglycine diacetic acid (MGDA) and / or its salts as complexing agents, wherein the amount of methylglycine diacetic acid (MGDA) and its salts is preferably 4.5 to 20 wt.%, based on the weight of the total composition.

5. Use of a dishwashing detergent formulation according to any one of claims 1 to 4, characterized by the fact that The thickening agent is selected from polysaccharides, in particular xanthan gum, urea derivatives and cross-linked polyacrylic acids.

6. Use of a dishwashing detergent formulation according to claim 5, characterized by the fact that The thickening agent xanthan gum is preferably used in an amount of 0.2 to 0.8 wt.% of the total composition.

7. Use of a dishwashing detergent formulation according to any one of claims 1 to 6, wherein the monomer (b3) is at least one compound of the general formula (I), where the variables are defined as follows: Z is O or NR1, R1 is selected from methyl and hydrogen, A1 is selected from C2-C4 alkylenes, R2 are the same or different and selected from C1-C4 alkylenes, X - is selected from halide, mono-C1-C4 alkyl sulfate and sulfate.

8. Use of a dishwashing detergent formulation according to claim 7, wherein the monomer (b3) is trimethylaminoethyl(meth)acrylatochloride or methacrylamidopropyltrimethylammonium chloride, preferably ω-trimethylaminoethyl(meth)acrylatochloride.

9. Use of a dishwashing detergent formulation according to any one of claims 1 to 8, characterized by the fact thatThe composition, in each case based on the weight of the total composition, comprises: (i) 1 - 4 wt.-% of a) at least one of polyaspartic acid or modified polyaspartic acid or their salts, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% at least one carboxyl-containing compound other than aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1; (ii) 5 - 20 wt.-% citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iii) 0.2 - 0.8 wt% xanthan gum; (iv) at least 20 wt% water; (v) 1 - 5 wt% non-ionic surfactants and (vi) 0.001 - 3 wt% enzymes.

10. Use of a dishwashing detergent formulation according to any one of claims 1 to 9, characterized by the fact that The composition has a pH value of 7.0 to 8.5, preferably 7.5 to 8.0, at 20 °C.

11. Use of a dishwashing detergent formulation according to any one of claims 1 to 10, characterized by the fact that the composition comprises amylases in an amount of 0.05 to 20 mg of active enzyme protein per gram of the total composition, preferably 0.07 to 10 mg of active enzyme protein per gram of the total composition, most preferably 0.10 to 2 mg of active enzyme protein per gram of the total composition.

12. Use of a dishwashing detergent formulation according to any one of claims 1 to 11, characterized by the fact that The composition comprises proteases in an amount of 0.1 to 50 mg of active enzyme protein per gram of the total composition, preferably 0.2 to 25 mg of active enzyme protein per gram of the total composition, or 0.5 to 10 mg of active enzyme protein per gram of the total composition.

13. Use of a dishwashing detergent formulation comprising at least two compositions A and B which are liquid at 20 °C, wherein composition A (enzyme phase) comprises: (i) 1 - 5 wt.-% of the total composition A from (a) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound other than aspartic acid, and subsequent hydrolysis of the cocondensates upon addition of a base, (b) at least one graft copolymer comprising (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains formed by grafting (b2) at least one ethylene-unsaturated mono- or dicarboxylic acid and (b3) at least one ethylene-unsaturated nitrogen-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is between 18:1 and 5:1, preferably of 11:1 to 8:1, particularly preferably 11:1 to 9:1; (ii) 3 to 30 wt.(iii) 0.1 to 2 wt.% of total composition A of complexing agents selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), ethylenediamine diacetic acid (EDDS), glutamic acid diacetic acid (GLDA) and / or their salts; (iii) 0.1 to 2 wt.% of total composition A of thickening agents, preferably selected from polysaccharides, in particular xanthan gum; (iv) 0.5 to 8 wt.% of total composition A of nonionic surfactants; (v) 0.001 to 3 wt.% of total composition A of enzymes; (vi) 0 to 15 wt.% of the total composition A of other builders and / or co-builders than ii) (vii) 0 to 30 wt.% of the total composition A of organic solvents and (viii) at least 20 wt.% water, wherein the composition A is preferably a composition according to claims 1 to 12, AND wherein the composition B (alkaline phase), in each case based on the total weight of the composition B, comprises: (ix) 3 to 30 wt.% of the total composition A.(x) Complexing agent selected from the group consisting of citric acid, methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), EDDS and / or their salts as complexing agents; (x) 1 to 20% wt% builder and / or cobuilder, which are not identical to the complexing agents according to (ix); (xi) 0.15 to 2% wt% thickener, preferably selected from polysaccharides, in particular xanthan gum; (xii) optionally 0.01 to 3% wt% anionic surfactant, preferably selected from the group consisting of alkyl sulfonates, alkyl sulfates and alkylbenzenesulfonates; and (xiii) at least 20% wt% water. for improving cleaning performance on stubborn carbohydrate-containing soils, preferably baked-on and / or burnt-on carbohydrate-containing soils, in particular protein- and carbohydrate-containing soils, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soils.

14. Methods for machine dishwashing, characterized by the fact thata cleaning agent according to one of claims 1 to 13 is brought into contact with items being washed which have stubborn carbohydrate-containing soiling, preferably baked-on and / or burnt-on carbohydrate-containing soiling, in particular protein- and carbohydrate-containing soiling, especially preferably baked-on and / or burnt-on protein- and carbohydrate-containing soiling.

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